EP0443138A1 - Polyisocyanate mixtures, process for their preparation and their use as a binder for coating-compositions or as a reaction component for compounds reactive with isocyanate groups or carboxylic groups - Google Patents
Polyisocyanate mixtures, process for their preparation and their use as a binder for coating-compositions or as a reaction component for compounds reactive with isocyanate groups or carboxylic groups Download PDFInfo
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- EP0443138A1 EP0443138A1 EP90124222A EP90124222A EP0443138A1 EP 0443138 A1 EP0443138 A1 EP 0443138A1 EP 90124222 A EP90124222 A EP 90124222A EP 90124222 A EP90124222 A EP 90124222A EP 0443138 A1 EP0443138 A1 EP 0443138A1
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- polyisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
Definitions
- the invention relates to new polyisocyanate mixtures which have both carboxyl groups and (cyclo) aliphatic-bonded uretdione groups and which therefore represent versatile precursors for the production of plastics.
- Process for the preparation of these polyisocyanate mixtures by modifying organic polyisocyanates with (cyclo) aliphatic-bonded isocyanate groups aliphatic hydroxycarboxylic acids with the use of polyisocyanates containing uretdione groups or by modification of organic polyisocyanates with hydroxycarboxylic acids and subsequent dimerization of part of the remaining isocyanate groups and the use of the polyisocyanate mixtures as binders for coating agents or as reactants for compounds which are reactive towards isocyanate or carboxyl groups in the production of high molecular weight polymers .
- Polyisocyanates containing uretdione groups are interesting, heat-activatable, cleavage-free crosslinking agents for plastic precursors with groups that are reactive towards isocyanate groups, since they react with them both at room temperature (free NCO groups) and at higher temperatures (blocked NCO groups) in the sense of an addition reaction able to react.
- allophanate groups are formed from hydroxyl groups and uretdione groups at elevated temperatures.
- Compounds with cycloaliphatically bound uretdione groups (DE-AS 3 030 513) or with aliphatically bound uretdione groups (DE-OS 3 437 635).
- plastic precursors Compounds containing isocyanate groups and free carboxyl groups have also become known as plastic precursors.
- plastic precursors for example, in the synthesis of aqueous polyurethane dispersions by using sterically hindered hydroxyalkane carboxylic acids - such as e.g. Dimethylolpropionic acid - built-in carboxyl-bearing NCO polyurethane prepolymers are prepared as intermediates (US Pat. No. 3,412,054).
- polyisocyanate mixtures according to the invention described in more detail below are at room temperature despite the simultaneous presence Isocyanate and carboxyl groups are stable in storage for at least 3 months, they are soluble or dispersible in water in neutralized form with tertiary amines, they are self-crosslinking in the heat, they have the interesting property, even without the addition of other auxiliaries and additives to be film-forming and, of course, because of the simultaneous presence of three different reactive groups, they are accessible to a wide variety of reactions with corresponding reaction partners. They are particularly suitable in combination with compounds having groups which are reactive toward isocyanate groups for the production of interesting high-molecular plastics.
- the invention also relates to a first process for producing these polyisocyanates by reacting a polyisocyanate component A) consisting of at least one polyisocyanate with (cyclo) aliphatically bonded isocyanate groups of the molecular weight range 168 to 1000 with a hydroxycarboxylic acid component B) consisting of at least one aliphatic Hydroxycarboxylic acid in the molecular weight range 76 to 200, optionally with the use of further reactants with aliphatically bound hydroxyl groups that are reactive towards isocyanate groups, while maintaining an equivalent ratio of isocyanate groups to hydroxyl groups of 1.05: 1 to 80: 1 and, if appropriate, subsequent distillative removal of volatile, unreacted Starting polyisocyanates and / or possibly subsequent mixing of the resulting reaction product with further organic polyisocyanates C), characterized in that the polyisocyanate at component A) or as part of the polyisocyanate component A) and / or as polyisocyanates C) or as part
- the invention further relates to a second process for the preparation of these polyisocyanates, which is characterized in that a polyisocyanate component A) consisting of at least one is essentially Uretdione group-free polyisocyanate with (cyclo) aliphatically bound isocyanate groups in the molecular weight range 168 to 1000 with a hydroxycarboxylic acid component B) consisting of at least one aliphatically bound hydroxycarboxylic acid in the molecular weight range 76 to 200, optionally with the use of further reaction partners with aliphatically bound to isocyanate groups Hydroxyl groups while maintaining an equivalent ratio of isocyanate groups to hydroxyl groups of 1.05: 1 to 400: 1, the remaining isocyanate groups of the reaction product to 5 to 60% in the presence of a catalyst that accelerates the dimerization of isocyanate groups into uretdione groups and, if appropriate, isocyanurate groups, which is then present If necessary, the reaction mixture is freed from excess starting
- the invention also relates to the use of the polyisocyanate mixtures, optionally in at least partially neutralized form with tertiary amines, as binders for coating compositions which can be crosslinked under the influence of moisture and / or heat.
- the invention also relates to the use of the polyisocyanate mixtures, if appropriate in at least partially neutralized form with tertiary amines, as reactants for compounds having groups which are reactive towards isocyanate groups and / or carboxyl groups in the production of high molecular weight plastics.
- the polyisocyanate component A) to be used in the first process according to the invention consists of at least one polyisocyanate of the molecular weight range 168 to 1000 with (cyclo) aliphatically bound isocyanate groups and an NCO functionality of 2 to 4, preferably 2 to 3.
- simple organic diisocyanates such as, for example, are suitable 1,6-diisocyanatohexane (HDI), 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), 4,4'-diisocyanato-dicyclohexylmethane or modification products of such simple diisocyanates such as polyisocyanates with oxadiazinetrione structure such as they are formed from 2 moles of such a diisocyanate, in particular 2 moles of HDI with 1 mole of carbon dioxide, polyisocyanates containing biuret groups such as in particular N, N ', N''- tris (isocyanatohexyl) biuret or mixtures thereof with its higher homologues or polyisocyanates containing isocyanurate groups based on the simple diisocyanates mentioned by way of example, especially based on HDI and nd / or IPDI or uretd
- the hydroxycarboxylic acid component B) to be used in both methods according to the invention consists of at least one aliphatic hydroxycarboxylic acid of the molecular weight range 76 to 200, such as 2-hydroxyacetic acid, 4-hydroxybutyric acid, 2,2-bis (hydroxymethyl) propionic acid (DMPS). DMPS is particularly preferably used as the hydroxycarboxylic acid component B).
- further structural components with aliphatically bound hydroxyl groups can optionally be used as further reactants.
- These compounds are preferably nonionically hydrophilic structural components which contribute to the hydrophilicity of the polyisocyanate mixtures according to the invention.
- diols having hydrophilic side chains of the type mentioned in US Pat. No. 4,190,566 or hydrophilic monohydric polyether alcohols of the type mentioned in US Pat. No. 4,237,264 should be mentioned by way of example.
- aliphatic hydroxyl groups are, for example, low molecular weight chain extenders or crosslinking agents such as ethylene glycol, propylene glycol, trimethylolpropane or mixtures of such low molecular weight polyhydroxyl compounds, which generally have a maximum molecular weight of 200.
- Emulsifiers of the type known per se such as, for example, ethoxylated alkylphenols, in particular ethoxylated nonylphenols, or built-in emulsifiers having ether or ester groups, such as, for example, polyoxyethylene lauryl ether or polyoxyethylene esters of higher fatty acids such as, for example, polyoxyethylene laurate, oleate or stearate, can be used as a further structural component with an aliphatic hydroxyl group can also be used.
- emulsifiers which can be incorporated generally have 8 to 50 oxyethylene units per molecule.
- the reaction of the starting materials mentioned by way of example is generally carried out while maintaining an equivalent ratio of isocyanate groups to hydroxyl groups of 1.05: 1 to 80: 1, preferably 1.2: 1 to 50: 1 at 20 to 100 , preferably 25 to 90 ° C.
- the reaction can be carried out in bulk or in the presence of suitable solvents which are inert to isocyanate groups.
- reaction products of both processes according to the invention can optionally be mixed with further organic polyisocyanates C).
- Suitable other Polyisocyanates are, in particular, polyisocyanates containing uretdione groups with aliphatically bound uretdione groups of the type already mentioned above in connection with component A).
- Other conceivable blending components are, for example, aromatic uretdione diisocyanates such as, for example, dimerized or trimerized 2,4-diisocyanatotoluene or other polyisocyanates derived from polyurethane chemistry per se known type, for example those as already mentioned above as starting component A) for the inventive method.
- the type and quantitative ratios of the reactants and the type and amount of the polyisocyanates C) which may be subsequently added are dimensioned within the scope of the disclosure made such that the resulting polyisocyanate mixtures according to the invention correspond to the information given above a) to d) correspond.
- the particularly preferred polyisocyanate mixtures according to the invention have an average NCO functionality of 1.5 to 4, in particular 1.5 to 3, an NCO content of 2 to 40, in particular 5 to 20% by weight, a carboxyl group content of 0.01 to 15, in particular 0.5 to 5% by weight, and a content of aliphatically bound uretdione groups of 1 to 23, in particular 5 to 20% by weight.
- a second reaction step 5 to 60%, preferably 10 to 50%, preferably 10 to 50% of the isocyanate groups of the reaction mixture obtained are converted into uretdione groups and optionally isocyanurate groups in the presence of a catalyst which accelerates the dimerization of isocyanate groups.
- a catalyst which accelerates the dimerization of isocyanate groups.
- This oligomerization reaction generally takes place in the temperature range from 25 to 100, preferably 25 to 90 ° C., the ratio of uretdione groups to isocyanurate groups in the oligomerization product being able to be controlled by suitable choice of the catalyst and in particular the reaction temperature.
- Suitable catalysts are the tertiary phosphines known per se (DE-OS 1 670 720, 1 934 763, 3 030 513 or US Pat. No. 4,614,785). Tri-n-butyl- or tri-n-octylphosphine are particularly suitable.
- the oligomerization reaction is stopped in a manner known per se using suitable catalyst poisons, e.g. p-Toluenesulfonic acid methyl ester or sulfur or else by distillative removal of the catalyst from the reaction mixture.
- suitable catalyst poisons e.g. p-Toluenesulfonic acid methyl ester or sulfur or else by distillative removal of the catalyst from the reaction mixture.
- the starting polyisocyanate A) which is still present in excess is optionally removed, for example by thin-layer distillation, and, if appropriate, a subsequent mixing with further organic polyisocyanates C).
- the type and proportions of the reactants and the amount of the starting polyisocyanate A) which may have been removed following the reaction, and the type and amount of the optionally admixed polyisocyanate C) are such that the resulting polyisocyanate mixtures according to the invention correspond to the information given above a ) to d) correspond.
- the statements made above with regard to the key figures of the particularly preferred polyisocyanate mixtures according to the invention also apply to the process products of the second process according to the invention.
- the polyisocyanate mixtures according to the invention provide valuable, versatile applications Intermediates or crosslinkers in the manufacture of high molecular weight plastics.
- the polyisocyanate mixtures according to the invention can e.g. by neutralizing part or all of the carboxyl groups with, for example, tert. Amines are converted into a water-dispersible or soluble form.
- amines are tert-inert to isocyanate groups.
- Amines such as triethylamine, N-methylpyrrolidine, N-methylpiperidine or N-methylmorpholine or tert reactive towards isocyanate groups.
- Amines, especially amino alcohols such as triethanolamine, N-methyl-diethanolamine, 2- (N, N-dimethylamino) iso-propanol or N, N-dimethylethanolamine.
- aqueous solutions or dispersions of self-crosslinking binders result which, under the influence of the water in the sense of a chain extender, react to form film-forming solutions or dispersions of high molecular weight plastics (cf. Example 1).
- the polyisocyanate mixtures according to the invention which are optionally at least partially neutralized, are self-crosslinking binders under the influence of moisture or heat and can be stored at room temperature practically indefinitely.
- polyisocyanate mixtures according to the invention can also be reacted with the higher molecular weight polyhydroxyl compounds known per se from polyurethane chemistry to give high molecular weight polyurethanes in which, in addition to free isocyanate groups, the uretdione groups or carboxyl groups are present as further reactive centers, so that the polyurethanes are accessible to further reactions, in particular crosslinking reactions with suitable reaction partners are.
- the polyisocyanate mixtures according to the invention can also be added as reactive emulsifiers to aqueous polymer dispersions in order to improve their level of properties.
- auxiliaries and additives customary in paint technology can of course also be used. These include, for example, pigments, fillers, solvents, flow control agents, plasticizers and the like.
- a polyisocyanate mixture consisting of a mixture of uretdione diisocyanate and isocyanurate group-containing polyisocyanate, each based on 1,6-diisocyanatohexane (HDI) with an NCO content of 21.6%, an average NCO functionality of 2.3 and a viscosity of 150 mPa.s / 23 ° C. 46.90 g dimethylolpropionic acid (DMPS) and 30.6 g of N-methylmorpholine (NMM) are mixed with stirring and kept at 70 ° C. until the titrimetrically determined NCO content of the reaction mixture has dropped to 15.3%.
- HDI 1,6-diisocyanatohexane
- DMPS dimethylolpropionic acid
- NMM N-methylmorpholine
- a polyisocyanate mixture according to the invention is partially in the salt form.
- the solution of the polyisocyanate mixture according to the invention, partly in salt form, placed on a glass plate dries to a clear, after 2 hours at room temperature or 30 minutes at 140 ° C. elastic, tear and tack free film.
- the König pendulum hardness is 40 s for the film dried at room temperature and 70 s for the film cured with heat.
- a film of the starting polyisocyanate mixture drawn on a glass plate for comparison remains liquid under the same drying conditions.
- the storage stability of the partially neutralized polyisocyanate mixture according to the invention was checked by titrating the NCO content and determining the viscosity as a function of the storage time at room temperature:
- aqueous dispersion 450 g of the partially neutralized polyisocyanate mixture according to the invention are mixed with 550 g of deionized water with vigorous stirring. A bluish, aqueous dispersion is formed which is stirred at room temperature for 1 h until the evolution of gas has ended.
- the films of the aqueous polyurethane / urea dispersion dried at room temperature (a) and at 140 ° C. (b) are clear, crack-free and elastic.
- the König pendulum hardness is 50 (a) or 80 s (b).
- the polyisocyanate mixture dries on glass plates to form clear, hard films.
- the König pendulum hardness is 65 s after room temperature drying and 85 s after oven drying.
- the storage stability test of the polyisocyanate mixture according to the invention at room temperature showed an NCO content of 8.30% and a viscosity of 975 mPa.s. after 150 days.
- a film of the mixture applied to a glass plate dries after about 2 hours at room temperature until it is tack-free and forms a clear, glossy and trouble-free lacquer film which, after complete curing, has a König pendulum hardness of 130 s. After one minute of exposure to aliphatic hydrocarbons, the film surface remains unchanged. When xylene, methoxypropyl acetate and ethanol are exposed for an equally long time, the surface of the paint swells slightly, with the film regenerating after the solvents have evaporated.
- a film produced accordingly but without the use of the polyisocyanate solution according to the invention, swells significantly even when exposed to aliphatic hydrocarbons and is readily soluble in aromatic hydrocarbons or methoxypropyl acetate.
- the processing time of the two-component system according to the invention containing the polyisocyanate solution according to the invention is about 4 hours.
- the polyisocyanate mixture is a mixture of 15.2 g of a polyisocyanate containing isocyanurate groups and based on 1,6-diisocyanatohexane with an NCO functionality of 3.5, an NCO content of 21.7% and a viscosity at 23 ° C of 1,500 mPa.s and 15.2 g of the polyisocyanate mixture according to Example 2, which has been neutralized beforehand with 1.3 g of N, N-dimethylethanolamine.
- NCO / OH equivalent ratio 1.5: 1.
- a paint film obtained from the formulation is tack-free, high-gloss and trouble-free after 2 hours at room temperature. If the polyacrylate resin is cured solely with the polyisocyanate mentioned, which has isocyanurate groups, films are obtained with a clear cloudiness and reduced gloss.
- the lacquer film according to the invention After curing at room temperature, the lacquer film according to the invention has a König hardness of 150 s. At 1 minute exposure to aliphatic or aromatic hydrocarbons or methoxypropyl acetate shows no change in the film surface. When ethanol is exposed for the same period of time, there is a slight swelling that is reversible after the solvent has evaporated.
- HDI hexamethylene diisocyanate
- DMPS dimethylpropionic acid
- reaction is then stopped by adding 4.1 g of p-toluenesulfonic acid methyl ester (TSE) and stirring at 80 ° C. for one hour.
- TSE p-toluenesulfonic acid methyl ester
- the excess HDI is then removed from the raw material solution by vacuum distillation using a short-path evaporator at 150 ° C./0.05 mbar.
- the 100% polyisocyanate mixture according to the invention dries on a glass plate after 1 hour at room temperature or 30 minutes at 140 ° C. to form a clear, crack-free and dust-dry film.
- the König pendulum hardness is 60 s for the film dried at room temperature and 85 s for the heat-cured film.
- IPDI isophorone diisocyanate
- reaction is then stopped by adding 4.1 g of TSE and stirring at 80 ° C. for one hour.
- the examination of the storage stability of the carboxyl polyisocyanate according to the invention showed an NCO content of 18.2% and a viscosity of 3295 mPas after 150 days at room temperature.
- the carboxyl polyisocyanate according to the invention dries on a glass plate after 1 hour at room temperature or 30 minutes at 140 ° C. to form a clear, crack-free film.
- the König pendulum hardness after drying at room temperature is 80 s, for the oven-dried 98 s.
- Example 2 505.4 g of the starting polyisocyanate based on HDI described in Example 1 are mixed with 579.0 g of a uretdione / isocyanurate polyisocyanate based on 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (IPDI) mixed.
- IPDI 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane
- the resulting clear solution has an NCO content of 20.2%, a viscosity of 1320 mPas (23 ° C) and an average functionality of 2.3. is stirred at 74 ° C until the NCO content of the reaction mixture has dropped to 14.9%.
- the films of the polyisocyanate mixture according to the invention prepared and dried as in Example 1 are clear and homogeneous.
- the König pendulum hardness is 85 s after 2 h room temperature drying and 108 s after 30 min oven drying. After one minute of exposure to aliphatic and aromatic hydrocarbons and methoxypropyl acetate, the film surface of the cured polyisocyanate mixture remains unchanged.
- the examination of the storage stability of the polyisocyanate mixture showed an NCO content of 14.6% and a viscosity of 1811 mPas (23 ° C.) after 150 days at room temperature.
- the polyisocyanates according to the invention can be dispersed spontaneously as described in Example 1.
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Abstract
Description
Die Erfindung betrifft neue Polyisocyanatgemische, die sowohl Carboxylgruppen als auch (cyclo)aliphatisch gebundene Uretdiongruppen aufweisen, und die daher vielseitig verwendbare Vorprodukte für die Herstellung von Kunststoffen darstellen, Verfahren zur Herstellung dieser Polyisocyanatgemische durch Modifizierung von organischen Polyisocyanaten mit (cyclo)aliphatisch gebundenen Isocyanatgruppen mit aliphatischen Hydroxycarbonsäuren unter Mitverwendung von Uretdiongruppen aufweisenden Polyisocyanaten oder durch Modifizierung von organischen Polyisocyanaten mit Hydroxycarbonsäuren und anschließende Dimerisierung eines Teils der verbleibenden Isocyanatgruppen und die Verwendung der Polyisocyanatgemische als Bindemittel für Überzugsmittel oder als Reaktionspartner für gegenüber Isocyanat- oder Carboxylgruppen reaktionsfähige Verbindungen bei der Herstellung von hochmolekularen Kunststoffen.The invention relates to new polyisocyanate mixtures which have both carboxyl groups and (cyclo) aliphatic-bonded uretdione groups and which therefore represent versatile precursors for the production of plastics. Process for the preparation of these polyisocyanate mixtures by modifying organic polyisocyanates with (cyclo) aliphatic-bonded isocyanate groups aliphatic hydroxycarboxylic acids with the use of polyisocyanates containing uretdione groups or by modification of organic polyisocyanates with hydroxycarboxylic acids and subsequent dimerization of part of the remaining isocyanate groups and the use of the polyisocyanate mixtures as binders for coating agents or as reactants for compounds which are reactive towards isocyanate or carboxyl groups in the production of high molecular weight polymers .
Uretdiongruppen aufweisende Polyisocyanate stellen interessante, hitze-aktivierbare, abspalterfreie Vernetzungsmittel für Kunststoffvorläufer mit gegenüber Isocyanatgruppen reaktionsfähigen Gruppen dar, da sie sowohl bei Raumtemperatur (freie NCO-Gruppen) als auch bei höheren Temperaturen (blockierte NCO-Gruppen) mit diesen im Sinne einer Additionsreaktion zu reagieren vermögen. So entstehen beispielsweise aus Hydroxylgruppen und Uretdiongruppen bei erhöhten Temperaturen Allophanatgruppen. Von technischer Bedeutung sind hierbei u.a. Verbindungen mit cycloaliphatisch gebundenen Uretdiongruppen (DE-AS 3 030 513) bzw, mit aliphatisch gebundenen Uretdiongruppen (DE-OS 3 437 635).Polyisocyanates containing uretdione groups are interesting, heat-activatable, cleavage-free crosslinking agents for plastic precursors with groups that are reactive towards isocyanate groups, since they react with them both at room temperature (free NCO groups) and at higher temperatures (blocked NCO groups) in the sense of an addition reaction able to react. For example, allophanate groups are formed from hydroxyl groups and uretdione groups at elevated temperatures. The following are of technical importance: Compounds with cycloaliphatically bound uretdione groups (DE-AS 3 030 513) or with aliphatically bound uretdione groups (DE-OS 3 437 635).
Auch Isocyanatgruppen und freie Carboxylgruppen aufweisende Verbindungen sind als Kunststoffvorläufer bekannt geworden. So können beispielsweise bei der Synthese wäßriger Polyurethandispersionen durch Verwendung sterisch gehinderter Hydroxyalkancarbonsäuren - wie z.B. Dimethylolpropionsäure - eingebaute Carboxylgruppen tragende NCO-Polyurethanprepolymere als Zwischenstufen hergestellt werden (US-P 3 412 054).Compounds containing isocyanate groups and free carboxyl groups have also become known as plastic precursors. For example, in the synthesis of aqueous polyurethane dispersions by using sterically hindered hydroxyalkane carboxylic acids - such as e.g. Dimethylolpropionic acid - built-in carboxyl-bearing NCO polyurethane prepolymers are prepared as intermediates (US Pat. No. 3,412,054).
Überraschenderweise wurde jetzt gefunden, daß die Kombination dieser beiden Prinzipien, d.h, der gleichzeitige Einbau von (cyclo)aliphatisch gebundenen Uretdiongruppen und Carboxylgruppen zu entsprechend modifizierten Polyisocyanatgemischen führt, die eine Reihe bemerkenswerter Eigenschaften in sich vereinen. Diese nachstehend näher beschriebenen erfindungsgemäßen Polyisocyanatgemische sind bei Raumtemperatur trotz des gleichzeitigen Vorliegens von Isocyanat- und Carboxylgruppen während mindestens 3 Monaten lagerstabil, sie sind in mit tert.- Aminen neutralisierter Form in Wasser löslich bzw. dispergierbar, sie sind in der Hitze selbstvernetzend, sie weisen die interessante Eigenschaft auf, auch ohne Zusatz weiterer Hilfs- und Zusatzmittel filmbildend zu sein, und sie sind selbstverständlich wegen des gleichzeitigen Vorliegens von drei unterschiedlichen Reaktivgruppen den unterschiedlichsten Reaktionen mit entsprechenden Reaktionspartnern zugänglich. Insbesondere eignen sie sich in Kombination mit Verbindungen mit gegenüber Isocyanatgruppen reaktionsfähigen Gruppen zur Herstellung von interessanten hochmolekularen Kunststoffen.Surprisingly, it has now been found that the combination of these two principles, ie the simultaneous incorporation of (cyclo) aliphatically bonded uretdione groups and carboxyl groups, leads to appropriately modified polyisocyanate mixtures which combine a number of remarkable properties. These polyisocyanate mixtures according to the invention described in more detail below are at room temperature despite the simultaneous presence Isocyanate and carboxyl groups are stable in storage for at least 3 months, they are soluble or dispersible in water in neutralized form with tertiary amines, they are self-crosslinking in the heat, they have the interesting property, even without the addition of other auxiliaries and additives to be film-forming and, of course, because of the simultaneous presence of three different reactive groups, they are accessible to a wide variety of reactions with corresponding reaction partners. They are particularly suitable in combination with compounds having groups which are reactive toward isocyanate groups for the production of interesting high-molecular plastics.
Gegenstand der Erfindung sind Polyisocyanatgemische, gekennzeichnet durch
- a) eine mittlere NCO-Funktionalität von 1,5 bis 4,0,
- b) einen Gehalt an (cyclo)aliphatisch gebundenen Isocyanatgruppen (NCO, Molekulargewicht = 42) von 2 bis 40 Gew.-%,
- c) einen Gehalt an chemisch fixierten Carboxylgruppen (COOH, Molekulargewicht = 45) von 0,01 bis 15 Gew.-% und
- d) einen Gehalt an (cyclo)aliphatisch gebundenen Uretdiongruppen (C₂N₂O₂, Molekulargewicht = 84) von 1 bis 23 Gew.-%.
- a) an average NCO functionality of 1.5 to 4.0,
- b) a content of (cyclo) aliphatically bound isocyanate groups (NCO, molecular weight = 42) of 2 to 40% by weight,
- c) a content of chemically fixed carboxyl groups (COOH, molecular weight = 45) of 0.01 to 15 wt .-% and
- d) a content of (cyclo) aliphatically bound uretdione groups (C₂N₂O₂, molecular weight = 84) of 1 to 23 wt .-%.
Gegenstand der Erfindung ist auch ein 1. Verfahren zur Herstellung dieser Polyisocyanate durch Umsetzung einer Polyisocyanatkomponente A), bestehend aus mindestens einem Polyisocyanat mit (cyclo)aliphatisch gebundenen Isocyanatgruppen des Molekulargewichtsbereichs 168 bis 1000 mit einer Hydroxycarbonsäure-Komponente B), bestehend aus mindestens einer aliphatischen Hydroxycarbonsäure des Molekulargewichtsbereichs 76 bis 200, gegebenenfalls unter Mitverwendung von weiteren Reaktionspartnern mit gegenüber Isocyanatgruppen reaktionsfähigen, aliphatisch gebundenen Hydroxylgruppen unter Einhaltung eines Äquivalentverhältnisses von Isocyanatgruppen zu Hydroxylgruppen von 1,05:1 bis 80:1 und gegebenenfalls anschließende destillative Entfernung von leicht flüchtigen, nicht umgesetzten Ausgangspolyisocyanaten und/oder gegebenenfalls anschließende Abmischung des resultierenden Umsetzungsprodukts mit weiteren organischen Polyisocyanaten C), dadurch gekennzeichnet, daß man als Polyisocyanatkomponente A) oder als Teil der Polyisocyanatkomponente A) und/oder als Polyisocyanate C) oder als Teil der Polyisocyanate C) (cyclo)aliphatisch gebundene Uretdiongruppen aufweisende Diisocyanate mit (cyclo)aliphatisch gebundenen Isocyanatgruppen verwendet, wobei im übrigen Art und Mengenverhältnisse der Reaktionspartner so gewählt werden, daß die resultierenden Polyisocyanatgemische den oben unter a) bis d) genannten Bedingungen entsprechen.The invention also relates to a first process for producing these polyisocyanates by reacting a polyisocyanate component A) consisting of at least one polyisocyanate with (cyclo) aliphatically bonded isocyanate groups of the molecular weight range 168 to 1000 with a hydroxycarboxylic acid component B) consisting of at least one aliphatic Hydroxycarboxylic acid in the molecular weight range 76 to 200, optionally with the use of further reactants with aliphatically bound hydroxyl groups that are reactive towards isocyanate groups, while maintaining an equivalent ratio of isocyanate groups to hydroxyl groups of 1.05: 1 to 80: 1 and, if appropriate, subsequent distillative removal of volatile, unreacted Starting polyisocyanates and / or possibly subsequent mixing of the resulting reaction product with further organic polyisocyanates C), characterized in that the polyisocyanate at component A) or as part of the polyisocyanate component A) and / or as polyisocyanates C) or as part of the polyisocyanates C) (cyclo) aliphatically bound uretdione groups containing diisocyanates with (cyclo) aliphatically bound isocyanate groups, the other type and proportions of the reactants so can be chosen so that the resulting polyisocyanate mixtures correspond to the conditions mentioned under a) to d).
Gegenstand der Erfindung ist ferner ein 2. Verfahren zur Herstellung dieser Polyisocyanate, welches dadurch gekennzeichnet ist, daß man eine Polyisocyanatkomponente A), bestehend aus mindestens einem, im wesentlichen Uretdiongruppen-freien Polyisocyanat mit (cyclo)aliphatisch gebundenen Isocyanatgruppen des Molekulargewichtsbereichs 168 bis 1000 mit einer Hydroxycarbonsäure-Komponente B), bestehend aus mindestens einer aliphatisch gebundenen Hydroxycarbonsäure des Molekulargewichtsbereichs 76 bis 200, gegebenenfalls unter Mitverwendung von weiteren Reaktionspartnern mit gegenüber Isocyanatgruppen reaktionsfähigen, aliphatisch gebundenen Hydroxylgruppen unter Einhaltung eines Äquivalentverhältnisses von Isocyanatgruppen zu Hydroxylgruppen von 1,05:1 bis 400:1 umsetzt, die verbleibenden Isocyanatgruppen des Umsetzungsprodukts zu 5 bis 60 % in Gegenwart eines die Dimerisierung von Isocyanatgruppen beschleunigenden Katalysators in Uretdiongruppen und gegebenenfalls Isocyanuratgruppen überführt, das dann vorliegende Reaktionsgemisch gegebenenfalls von überschüssigem Ausgangspolyisocyanate A) befreit und/oder mit weiteren organischen Polyisocyanaten C) abmischt, wobei Art und Mengenverhältnisse der Reaktionspartner und die Menge des gegebenenfalls am Ende der Umsetzung entfernten Ausgangspolyisocyanats A) und/oder des dem Reaktionsgemisch zugesetzten Polyisocyanat C) so bemessen werden, daß die resultierenden Polyisocyanatgemische den oben unter a) bis d) genannten Bedingungen entsprechen.The invention further relates to a second process for the preparation of these polyisocyanates, which is characterized in that a polyisocyanate component A) consisting of at least one is essentially Uretdione group-free polyisocyanate with (cyclo) aliphatically bound isocyanate groups in the molecular weight range 168 to 1000 with a hydroxycarboxylic acid component B) consisting of at least one aliphatically bound hydroxycarboxylic acid in the molecular weight range 76 to 200, optionally with the use of further reaction partners with aliphatically bound to isocyanate groups Hydroxyl groups while maintaining an equivalent ratio of isocyanate groups to hydroxyl groups of 1.05: 1 to 400: 1, the remaining isocyanate groups of the reaction product to 5 to 60% in the presence of a catalyst that accelerates the dimerization of isocyanate groups into uretdione groups and, if appropriate, isocyanurate groups, which is then present If necessary, the reaction mixture is freed from excess starting polyisocyanates A) and / or mixed with other organic polyisocyanates C), the type and quantitative ratio e of the reactants and the amount of the starting polyisocyanate A) and / or of the polyisocyanate C) added to the reaction mixture, if appropriate removed at the end of the reaction, are such that the resulting polyisocyanate mixtures correspond to the conditions mentioned under a) to d) above.
Gegenstand der Erfindung ist auch die Verwendung der Polyisocyanatgemische gegebenenfalls in zumindest teilweise mit tertiären Aminen neutralisierter Form als Bindemittel für unter dem Einfluß von Feuchtigkeit und/oder Hitze vernetzbaren Überzugsmitteln.The invention also relates to the use of the polyisocyanate mixtures, optionally in at least partially neutralized form with tertiary amines, as binders for coating compositions which can be crosslinked under the influence of moisture and / or heat.
Gegenstand der Erfindung ist schließlich auch die Verwendung der Polyisocyanatgemische gegebenenfalls in zumindest teilweise mit tertiären Aminen neutralisierter Form, als Reaktionspartner für Verbindungen mit gegenüber Isocyanatgruppen und/oder Carboxylgruppen reaktionsfähigen Gruppen bei der Herstellung von hochmolekularen Kunststoffen.Finally, the invention also relates to the use of the polyisocyanate mixtures, if appropriate in at least partially neutralized form with tertiary amines, as reactants for compounds having groups which are reactive towards isocyanate groups and / or carboxyl groups in the production of high molecular weight plastics.
Die beim 1. erfindungsgemäßen Verfahren einzusetzende Polyisocyanatkomponente A) besteht aus mindestens einem Polyisocyanat des Molekulargewichtsbereichs 168 bis 1000 mit (cyclo)aliphatisch gebundenen Isocyanatgruppen und einer NCO-Funktionalität von 2 bis 4, vorzugsweise 2 bis 3. Geeignet sind beispielsweise einfache organische Diisocyanate wie z.B. 1,6-Diisocyanatohexan (HDI), 1-Isocyanato-3,5,5-trimethyl-5-isocyanatomethyl-cyclohexan (IPDI), 4,4'-Diisocyanato-dicyclohexylmethan oder auch Modifizierungsprodukte derartiger einfacher Diisocyanate wie z.B. Polyisocyanate mit Oxadiazintrionstruktur wie sie aus 2 Mol eines derartigen Diisocyanats, insbesondere 2 Mol HDI mit 1 Mol Kohlendioxid entstehen, Biuretgruppen aufweisende Polyisocyanate wie insbesondere N,N',N''-Tris-(isocyanatohexyl)-biuret oder seine Gemische mit seinen höheren Homologen oder Isocyanuratgruppen aufweisende Polyisocyanate auf Basis der beispielhaft genannten einfachen Diisocyanate, insbesondere auf Basis von HDI und/oder IPDI oder Uretdiongruppen aufweisende Diisocyanate wie beispielsweise dimeres HDI oder dimeres IPDI oder beliebige Gemische derartiger Polyisocyanate, soweit sie den obengemachten Bedingungen entsprechen.The polyisocyanate component A) to be used in the first process according to the invention consists of at least one polyisocyanate of the molecular weight range 168 to 1000 with (cyclo) aliphatically bound isocyanate groups and an NCO functionality of 2 to 4, preferably 2 to 3. For example, simple organic diisocyanates such as, for example, are suitable 1,6-diisocyanatohexane (HDI), 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), 4,4'-diisocyanato-dicyclohexylmethane or modification products of such simple diisocyanates such as polyisocyanates with oxadiazinetrione structure such as they are formed from 2 moles of such a diisocyanate, in particular 2 moles of HDI with 1 mole of carbon dioxide, polyisocyanates containing biuret groups such as in particular N, N ', N''- tris (isocyanatohexyl) biuret or mixtures thereof with its higher homologues or polyisocyanates containing isocyanurate groups based on the simple diisocyanates mentioned by way of example, especially based on HDI and nd / or IPDI or uretdione group-containing diisocyanates such as dimeric HDI or dimeric IPDI or any mixtures of such polyisocyanates, insofar as they meet the above conditions.
Beim 2. erfindungsgemäßen Verfahren werden ausschließlich Ausgangspolyisocyanate A) der genannten Art eingesetzt, die keine Uretdiongruppen aufweisen, ansonsten jedoch den obengemachten Ausführungen entsprechen.In the second method according to the invention, only starting polyisocyanates A) of the type mentioned are used which have no uretdione groups, but otherwise correspond to the statements made above.
Die bei beiden erfindungsgemäßen Verfahren einzusetzende Hydroxycarbonsäurekomponente B) besteht aus mindestens einer aliphatischen Hydroxycarbonsäure des Molekulargewichtsbereichs 76 bis 200 wie beispielsweise 2-Hydroxyessigsäure, 4-Hydroxybuttersäure, 2,2-Bis-(hydroxymethyl)-propionsäure (DMPS). Besonders bevorzugt wird DMPS als Hydroxycarbonsäurekomponente B) verwendet.The hydroxycarboxylic acid component B) to be used in both methods according to the invention consists of at least one aliphatic hydroxycarboxylic acid of the molecular weight range 76 to 200, such as 2-hydroxyacetic acid, 4-hydroxybutyric acid, 2,2-bis (hydroxymethyl) propionic acid (DMPS). DMPS is particularly preferably used as the hydroxycarboxylic acid component B).
Bei der Durchführung beider erfindungsgemäßen Verfahren können als weitere Reaktionspartner gegebenenfalls weitere Aufbaukomponenten mit aliphatisch gebundenen Hydroxylgruppen eingesetzt werden. Bei diesen Verbindungen handelt es sich vorzugsweise um nichtionisch hydrophile Aufbaukomponenten, die zur Hydrophilie der erfindungsgemäßen Polyisocyanatgemische beitragen. In diesem Zusammenhang sind beispielsweise hydrophile Seitenketten aufweisende Diole der in US-PS 4 190 566 genannten Art oder hydrophile einwertige Polyetheralkohole der in US-PS 4 237 264 genannten Art beispielhaft zu erwähnen. Weitere gegebenenfalls mitzuverwendende Verbindungen mit aliphatisch gebundenen Hydroxylgruppen sind beispielsweise niedermolekulare Kettenverlängerungsmittel oder Vernetzer wie Ethylenglykol, Propylenglykol, Trimethylolpropan oder Gemische derartiger niedermolekularer Polyhydroxylverbindungen, die im allgemeinen ein maximales Molekulargewicht von 200 aufweisen. Auch einbaufähige Emulgatoren der an sich bekannten Art wie beispielsweise ethoxylierte Alkylphenole, insbesondere ethoxylierte Nonylphenole, oder Ether- bzw. Estergruppen aufweisende einbaufähige Emulgatoren wie beispielsweise Polyoxyethylenlaurylether oder Polyoxyethylen-ester höherer Fettsäuren wie beispielsweise Polyoxyethylenlaurat, -oleat oder -stearat können als weitere Aufbaukomponente mit einer aliphatischen Hydroxylgruppe mitverwendet werden. Diese einbaufähigen Emulgatoren weisen im allgemeinen pro Molekül 8 bis 50 Oxyethyleneinheiten auf.When carrying out both processes according to the invention, further structural components with aliphatically bound hydroxyl groups can optionally be used as further reactants. These compounds are preferably nonionically hydrophilic structural components which contribute to the hydrophilicity of the polyisocyanate mixtures according to the invention. In this connection, for example, diols having hydrophilic side chains of the type mentioned in US Pat. No. 4,190,566 or hydrophilic monohydric polyether alcohols of the type mentioned in US Pat. No. 4,237,264 should be mentioned by way of example. Other compounds that may be used with aliphatic hydroxyl groups are, for example, low molecular weight chain extenders or crosslinking agents such as ethylene glycol, propylene glycol, trimethylolpropane or mixtures of such low molecular weight polyhydroxyl compounds, which generally have a maximum molecular weight of 200. Also installable Emulsifiers of the type known per se, such as, for example, ethoxylated alkylphenols, in particular ethoxylated nonylphenols, or built-in emulsifiers having ether or ester groups, such as, for example, polyoxyethylene lauryl ether or polyoxyethylene esters of higher fatty acids such as, for example, polyoxyethylene laurate, oleate or stearate, can be used as a further structural component with an aliphatic hydroxyl group can also be used. These emulsifiers which can be incorporated generally have 8 to 50 oxyethylene units per molecule.
Die beispielhaft genannten Verbindungen mit alkoholischen Hydroxylgruppen können bei der Durchführung beider erfindungsgemäßen Verfahren in Mengen von bis zu 10 Gew.-%, bezogen auf das Gewicht der Komponenten A) und B) mitverwendet werden,The compounds mentioned by way of example with alcoholic hydroxyl groups can also be used in amounts of up to 10% by weight, based on the weight of components A) and B), when carrying out the two processes according to the invention,
Bei der Durchführung des 1. erfindungsgemäßen Verfahrens erfolgt die Umsetzung der beispielhaft genannten Ausgangsmaterialien im allgemeinen unter Einhaltung eines Äquivalentverhältnisses von Isocyanatgruppen zu Hydroxylgruppen von 1,05:1 bis 80:1, vorzugsweise 1,2:1 bis 50:1 bei 20 bis 100, vorzugsweise 25 bis 90°C. Die Umsetzung kann in Substanz oder auch in Gegenwart von geeigneten, gegenüber Isocyanatgruppen inerten Lösungsmitteln durchgeführt werden.When carrying out the first method according to the invention, the reaction of the starting materials mentioned by way of example is generally carried out while maintaining an equivalent ratio of isocyanate groups to hydroxyl groups of 1.05: 1 to 80: 1, preferably 1.2: 1 to 50: 1 at 20 to 100 , preferably 25 to 90 ° C. The reaction can be carried out in bulk or in the presence of suitable solvents which are inert to isocyanate groups.
Im Anschluß an die erfindungsgemäße Umsetzung können die Umsetzungsprodukte beider erfindungsgemäßen Verfahren gegebenenfalls mit weiteren organischen Polyisocyanaten C) abgemischt werden. Geeignete weitere Polyisocyanate sind insbesondere Uretdiongruppen aufweisende Polyisocyanate mit aliphatisch gebundenen Uretdiongruppen der bereits oben in Zusammenhang mit der Komponente A) beispielhaft genannten Art. Weitere denkbare Abmischkomponenten sind beispielsweise aromatische Uretdiondiisocyanate wie beispielsweise dimerisiertes oder trimerisiertes 2,4-Diisocyanatotoluol oder sonstige Polyisocyanate der aus der Polyurethanchemie an sich bekannten Art, beispielsweise solchen, wie sie bereits oben als Ausgangskomponente A) für das erfindungsgemäße Verfahren beispielhaft erwähnt werden.Following the reaction according to the invention, the reaction products of both processes according to the invention can optionally be mixed with further organic polyisocyanates C). Suitable other Polyisocyanates are, in particular, polyisocyanates containing uretdione groups with aliphatically bound uretdione groups of the type already mentioned above in connection with component A). Other conceivable blending components are, for example, aromatic uretdione diisocyanates such as, for example, dimerized or trimerized 2,4-diisocyanatotoluene or other polyisocyanates derived from polyurethane chemistry per se known type, for example those as already mentioned above as starting component A) for the inventive method.
Bei der Durchführung des 1. erfindungsgemäßen Verfahrens werden die Art und Mengenverhältnisse der Reaktionspartner, sowie die Art und Menge der gegebenenfalls noch nachträglich zugemischten Polyisocyanate C) im Rahmen der gemachten Offenbarung so bemessen, daß die resultierenden erfindungsgemäßen Polyisocyanatgemische den obengemachten Angaben a) bis d) entsprechen. Die besonders bevorzugten erfindungsgemäßen Polyisocyanatgemische weisen eine mittlere NCO-Funktionalität von 1,5 bis 4, insbesondere 1,5 bis 3, einen NCO-Gehalt von 2 bis 40, insbesondere 5 bis 20 Gew.-%, einen Carboxylgruppengehalt von 0,01 bis 15, insbesondere 0,5 bis 5 Gew.%, und einen Gehalt an aliphatisch gebundenen Uretdiongruppen von 1 bis 23, insbesondere 5 bis 20 Gew.-%, auf.When carrying out the first process according to the invention, the type and quantitative ratios of the reactants and the type and amount of the polyisocyanates C) which may be subsequently added are dimensioned within the scope of the disclosure made such that the resulting polyisocyanate mixtures according to the invention correspond to the information given above a) to d) correspond. The particularly preferred polyisocyanate mixtures according to the invention have an average NCO functionality of 1.5 to 4, in particular 1.5 to 3, an NCO content of 2 to 40, in particular 5 to 20% by weight, a carboxyl group content of 0.01 to 15, in particular 0.5 to 5% by weight, and a content of aliphatically bound uretdione groups of 1 to 23, in particular 5 to 20% by weight.
Bei der Durchführung des 2. erfindungsgemäßen Verfahrens werden, wie bereits ausgeführt, als Ausgangspolyisocyanate A) ausschließlich solche eingesetzt, die im wesentlichen frei von Uretdiongruppen sind, Diese Ausgangspolyisocyanate werden dann mit Hydroxycarbonsäuren der oben beispielhaft genannten Art gegebenenfalls unter Mitverwendung von weiteren Verbindungen mit aliphatisch gebundenen Hydroxylgruppen der ebenfalls oben beispielhaft genannten Art unter Einhaltung eines NCO/OH-Äquivalentverhältnisses von 1,05:1 bis 400:1 zur Reaktion gebracht. Diese Umsetzung erfolgt vorzugsweise in Substanz bei 25 bis 90°C.When carrying out the second method according to the invention, as already stated, only those starting polyisocyanates A) are used which are essentially free of uretdione groups. These starting polyisocyanates are then optionally treated with hydroxycarboxylic acids of the type mentioned above With the use of further compounds with aliphatically bound hydroxyl groups of the type likewise mentioned above, the reaction was carried out while maintaining an NCO / OH equivalent ratio of 1.05: 1 to 400: 1. This reaction is preferably carried out in bulk at 25 to 90 ° C.
In einem 2. Reaktionsschritt werden die Isocyanatgruppen des hierbei anfallenden Reaktionsgemischs dann zu 5 bis 60 %, vorzugsweise zu 10 bis 50 % in Gegenwart eines die Dimerisierung von Isocyanatgruppen beschleunigenden Katalysators in Uretdiongruppen und gegebenenfalls Isocyanuratgruppen überführt. Dies bedeutet, daß bei dieser Oligomerisierungsreaktion bis zu 80 %, vorzugsweise bis zu 50 % der während der Reaktion umgesetzten Isocyanatgruppen in Isocyanuratgruppen und zum Rest in Uretdiongruppen überführt werden, wobei auch höhere und/oder gemischte Homologe der entsprechenden Oligomerisierungsprodukte entstehen können. Diese Oligomerisierungsreaktion erfolgt im allgemeinen im Temperaturbereich von 25 bis 100, vorzugsweise 25 bis 90°C, wobei durch geeignete Wahl des Katalysators und insbesondere der Reaktionstemperatur das Verhältnis von Uretdiongruppen zu Isocyanuratgruppen im Oligomerisierungsprodukt gesteuert werden kann.In a second reaction step, 5 to 60%, preferably 10 to 50%, preferably 10 to 50% of the isocyanate groups of the reaction mixture obtained are converted into uretdione groups and optionally isocyanurate groups in the presence of a catalyst which accelerates the dimerization of isocyanate groups. This means that in this oligomerization reaction up to 80%, preferably up to 50%, of the isocyanate groups reacted during the reaction are converted into isocyanurate groups and the rest into uretdione groups, with higher and / or mixed homologs of the corresponding oligomerization products also being able to be formed. This oligomerization reaction generally takes place in the temperature range from 25 to 100, preferably 25 to 90 ° C., the ratio of uretdione groups to isocyanurate groups in the oligomerization product being able to be controlled by suitable choice of the catalyst and in particular the reaction temperature.
Als Katalysatoren kommen die hierfür an sich bekannten tertiären Phosphine in Betracht (DE-OS 1 670 720, 1 934 763, 3 030 513 oder US-PS 4 614 785). Besonders gut geeignet sind Tri-n-butyl- oder Tri-n-octylphosphin.Suitable catalysts are the tertiary phosphines known per se (DE-OS 1 670 720, 1 934 763, 3 030 513 or US Pat. No. 4,614,785). Tri-n-butyl- or tri-n-octylphosphine are particularly suitable.
Die Abstoppung der Oligomerisierungsreaktion erfolgt in an sich bekannter Weise mittels geeigneter Katalysatorengifte wie z.B. p-Toluolsulfonsäuremethylester oder Schwefel oder aber auch durch destillative Entfernung des Katalysators aus dem Reaktionsgemisch.The oligomerization reaction is stopped in a manner known per se using suitable catalyst poisons, e.g. p-Toluenesulfonic acid methyl ester or sulfur or else by distillative removal of the catalyst from the reaction mixture.
Im Anschluß an die Oligomerisierungsreaktion erfolgt gegebenenfalls eine Entfernung des noch im Überschuß vorliegenden Ausgangspolyisocyanats A), beispielsweise durch Dünnschichtdestillation, sowie gegebenenfalls eine hieran anschließende Abmischung mit weiteren organischen Polyisocyanaten C).Following the oligomerization reaction, the starting polyisocyanate A) which is still present in excess is optionally removed, for example by thin-layer distillation, and, if appropriate, a subsequent mixing with further organic polyisocyanates C).
Auch beim 2. erfindungsgemäßen Verfahren werden Art und Mengenverhältnisse der Reaktionspartner, sowie die Menge des gegebenenfalls am Anschluß an die Umsetzung entfernten Ausgangspolyisocyanats A), sowie Art und Menge des gegebenenfalls zugemischten Polyisocyanats C) so bemessen, daß die resultierenden erfindungsgemäßen Polyisocyanatgemische den obengemachten Angaben a) bis d) entsprechen. Die obengemachten Ausführungen bezüglich der Kennzahlen der besonders bevorzugten erfindungsgemäßen Polyisocyanatgemische gelten auch für die Verfahrensprodukte des 2. erfindungsgemäßen Verfahrens.In the second method according to the invention, the type and proportions of the reactants and the amount of the starting polyisocyanate A) which may have been removed following the reaction, and the type and amount of the optionally admixed polyisocyanate C) are such that the resulting polyisocyanate mixtures according to the invention correspond to the information given above a ) to d) correspond. The statements made above with regard to the key figures of the particularly preferred polyisocyanate mixtures according to the invention also apply to the process products of the second process according to the invention.
Aufgrund des gleichzeitigen Vorliegens von drei unterschiedlichen Reaktionszentren stellen die erfindungsgemäßen Polyisocyanatgemische wertvolle, vielseitig anwendbare Zwischenprodukte bzw. Vernetzer bei der Herstellung von hochmolekularen Kunststoffen dar.Due to the simultaneous presence of three different reaction centers, the polyisocyanate mixtures according to the invention provide valuable, versatile applications Intermediates or crosslinkers in the manufacture of high molecular weight plastics.
Die erfindungsgemäßen Polyisocyanatgemische können z.B. durch Neutralisation eines Teils oder aller Carboxylgruppen mit beispielsweise tert. Aminen in eine wasserdispergierbare oder -lösliche Form überführt werden.The polyisocyanate mixtures according to the invention can e.g. by neutralizing part or all of the carboxyl groups with, for example, tert. Amines are converted into a water-dispersible or soluble form.
Für diese Neutralisationsreaktion geeignete tert. Amine sind beispielsweise gegenüber Isocyanatgruppen inerte tert. Amine wie Triethylamin, N-Methylpyrrolidin, N-Methylpiperidin oder N-Methylmorpholin oder gegenüber Isocyanatgruppen reaktionsfähige tert. Amine, insbesondere Aminoalkohole wie beispielsweise Triethanolamin, N-Methyl-diethanolamin, 2-(N,N-Dimethylamino)-iso-propanol oder N,N-Dimethylethanolamin.Suitable tert for this neutralization reaction. For example, amines are tert-inert to isocyanate groups. Amines such as triethylamine, N-methylpyrrolidine, N-methylpiperidine or N-methylmorpholine or tert reactive towards isocyanate groups. Amines, especially amino alcohols such as triethanolamine, N-methyl-diethanolamine, 2- (N, N-dimethylamino) iso-propanol or N, N-dimethylethanolamine.
Durch zumindest teilweise Neutralisation der Carboxylgruppen und anschließendes Lösen oder Dispergieren der erfindungsgemäßen Polyisocyanatgemische in Wasser resultieren wäßrige Lösungen oder Dispersionen von selbstvernetzenden Bindemitteln, die unter dem Einfluß des Wassers im Sinne eines Kettenverlängerungsmittels zu filmbildenden Lösungen oder Dispersionen hochmolekularer Kunststoffe ausreagieren (vgl. Beispiel 1). Im übrigen stellen die gegebenenfalls zumindest teilweise neutralisierten erfindungsgemäßen Polyisocyanatgemische unter dem Einfluß von Feuchtigkeit oder Hitze selbstvernetzende Bindemittel dar, die bei Raumtemperatur praktisch unbegrenzt lagerfähig sind.By at least partially neutralizing the carboxyl groups and then dissolving or dispersing the polyisocyanate mixtures according to the invention in water, aqueous solutions or dispersions of self-crosslinking binders result which, under the influence of the water in the sense of a chain extender, react to form film-forming solutions or dispersions of high molecular weight plastics (cf. Example 1). Otherwise, the polyisocyanate mixtures according to the invention, which are optionally at least partially neutralized, are self-crosslinking binders under the influence of moisture or heat and can be stored at room temperature practically indefinitely.
Die erfindungsgemäßen Polyisocyanatgemische können auch mit den aus der Polyurethanchemie an sich bekannten höhermolekularen Polyhydroxylverbindungen zu hochmolekularen Polyurethanen umgesetzt werden, in denen neben freien Isocyanatgruppen die Uretdiongruppen bzw. Carboxylgruppen als weitere reaktive Zentren vorliegen, so daß die Polyurethane weiteren Reaktionen, insbesondere Vernetzungsreaktionen mit geeigneten Reaktionspartnern zugänglich sind.The polyisocyanate mixtures according to the invention can also be reacted with the higher molecular weight polyhydroxyl compounds known per se from polyurethane chemistry to give high molecular weight polyurethanes in which, in addition to free isocyanate groups, the uretdione groups or carboxyl groups are present as further reactive centers, so that the polyurethanes are accessible to further reactions, in particular crosslinking reactions with suitable reaction partners are.
Die erfindungsgemäßen Polyisocyanatgemische können auch als reaktive Emulgatoren wäßrigen Polymerdispersionen zwecks Verbesserung ihres Eigenschaftsniveaus zugesetzt werden.The polyisocyanate mixtures according to the invention can also be added as reactive emulsifiers to aqueous polymer dispersions in order to improve their level of properties.
Im Falle der zumindest teilweisen Überführung der Carboxylgruppen in Carboxylatgruppen, insbesondere durch eine Teilneutralisation mit tert. Aminen, entstehen erfindungsgemäße Polyisocyanatgemische, die auf Grund des Vorliegens der so eingeführten basischen Zentren bei ihrer erfindungsgemäßen Verwendung oftmals eine erwünschte katalytische Wirkung auf die Isocyanat-Additionsreaktion ausüben.In the case of at least partial conversion of the carboxyl groups into carboxylate groups, in particular by partial neutralization with tert. Amines, polyisocyanate mixtures according to the invention are formed which, due to the presence of the basic centers thus introduced, often exert a desired catalytic effect on the isocyanate addition reaction when they are used according to the invention.
Bei der Verwendung der erfindungsgemäßen Polyisocyanatgemische insbesondere als Lackbindemittel oder als Zusatzmittel für Lacke können selbstverständlich die aus der Lacktechnologie üblichen Hilfs- und Zusatzmittel mitverwendet werden. Hierzu gehören beispielsweise Pigmente, Füllstoffe, Lösungsmittel, Verlaufhilfsmittel, Weichmacher u.dgl.When using the polyisocyanate mixtures according to the invention, in particular as paint binders or as additives for paints, the auxiliaries and additives customary in paint technology can of course also be used. These include, for example, pigments, fillers, solvents, flow control agents, plasticizers and the like.
In den nachfolgenden Beispielen beziehen sich alle Prozentangaben, soweit nichts anderslautendes angemerkt, auf Gewichtsprozente.In the following examples, all percentages, unless otherwise stated, relate to percentages by weight.
1010,67 g eines Polyisocyanatgemischs, bestehend aus einem Gemisch aus Uretdiondiisocyanat und Isocyanuratgruppen aufweisendem Polyisocyanat jeweils auf Basis von 1,6-Diisocyanatohexan (HDI) mit einem NCO-Gehalt von 21,6 %, einer mittleren NCO-Funktionalität von 2,3 und einer Viskosität von 150 mPa.s/23°C.
46,90 g Dimethylolpropionsäure (DMPS) und
30,6 g N-Methylmorpholin (NMM)
werden unter Rühren vermischt und solange bei 70°C gehalten, bis der titrimetrisch bestimmte NCO-Gehalt des Reaktionsgemischs auf 15,3 % abgefallen ist.1010.67 g of a polyisocyanate mixture consisting of a mixture of uretdione diisocyanate and isocyanurate group-containing polyisocyanate, each based on 1,6-diisocyanatohexane (HDI) with an NCO content of 21.6%, an average NCO functionality of 2.3 and a viscosity of 150 mPa.s / 23 ° C.
46.90 g dimethylolpropionic acid (DMPS) and
30.6 g of N-methylmorpholine (NMM)
are mixed with stirring and kept at 70 ° C. until the titrimetrically determined NCO content of the reaction mixture has dropped to 15.3%.
Nach Abkühlen auf Raumtemperatur liegt ein erfindungsgemäßes Polyisocyanatgemisch teilweise in der Salzform vor.
Die auf eine Glasplatte gegebene Lösung des erfindungsgemäßen, im teilweise in der Salzform vorliegenden Polyisocyanatgemischs trocknet nach 2 Stunden bei Raumtemperatur oder 30 Minuten bei 140°C zu einem klaren, elastischen, riß- und klebfreien Film. Die Pendelhärten nach König betragen für den bei Raumtemperatur getrockneten Film 40 s, für den bei Hitze gehärteten Film 70 s.The solution of the polyisocyanate mixture according to the invention, partly in salt form, placed on a glass plate dries to a clear, after 2 hours at room temperature or 30 minutes at 140 ° C. elastic, tear and tack free film. The König pendulum hardness is 40 s for the film dried at room temperature and 70 s for the film cured with heat.
Ein zum Vergleich auf eine Glasplatte gezogener Film des Ausgangspolyisocyanatgemischs bleibt unter den gleichen Trocknungsbedingungen flüssig.A film of the starting polyisocyanate mixture drawn on a glass plate for comparison remains liquid under the same drying conditions.
Die Überprüfung der Lagerstabilität des erfindungsgemäßen, teilweise neutralisierten Polyisocyanatgemisches erfolgte durch Titration des NCO-Gehalts und Bestimmung der Viskosität in Abhängigkeit von der Lagerzeit bei Raumtemperatur:
Zur Herstellung einer wäßrigen Dispersion werden 450 g des teilneutralisierten erfindungsgemäßen Polyisocyanatgemischs unter starkem Rühren mit 550 g entionisiertem Wasser versetzt. Es entsteht eine bläuliche, wäßrige Dispersion, die bis zum Ende der Gasentwicklung noch 1 h bei Raumtemperatur nachgerührt wird.
Die bei Raumtemperatur (a) und bei 140°C (b) getrockneten Filme der wäßrigen Polyurethan-/harnstoffdispersion sind klar, rißfrei und elastisch. Die Pendelhärten nach König liegen bei 50 (a) bzw. 80 s (b).The films of the aqueous polyurethane / urea dispersion dried at room temperature (a) and at 140 ° C. (b) are clear, crack-free and elastic. The König pendulum hardness is 50 (a) or 80 s (b).
100 g des teilneutralisierten Polyisocyanatgemisches werden in einem 2 l Erlenmeyerkolben vorgelegt, mit 30 g entionisiertem Wasser versetzt, kurz umgerührt und stehengelassen. Unter CO₂-Entwicklung entsteht innerhalb 1 min ein aufsteigender poröser Schaumpilz.100 g of the partially neutralized polyisocyanate mixture are placed in a 2 l Erlenmeyer flask, mixed with 30 g of deionized water, stirred briefly and left to stand. Under CO₂ development, an ascending porous foam develops within 1 min.
1010,67 g des Ausgangspolyisocyanatgemischs gemäß Beispiel 1, 167,5 g DMPS und 130 g N-Methylpyrrolidon (NMP) werden vermischt und bei 80°C solange gerührt, bis der titrimetrisch bestimmte NCO-Wert auf 8,6 % abgesunken ist. Nach Abkühlen auf Raumtemperatur liegt eine klare Lösung eines erfindungsgemäßen Polyisocyanatgemischs in NMP vor.
Das Polyisocyanatgemisch trocknet auf Glasplatten zu klaren, harten Filmen. Die Pendelhärten nach König liegen nach Raumtemperaturtrocknung bei 65 s, nach Ofentrocknung bei 85 s.The polyisocyanate mixture dries on glass plates to form clear, hard films. The König pendulum hardness is 65 s after room temperature drying and 85 s after oven drying.
Die Lagerstabilitätsprüfung des erfindungsgemäßen Polyisocyanatgemischs bei Raumtemperatur ergab nach 150 Tagen einen NCO-Gehalt von 8,30 % und eine Viskosität von 975 mPa.s.The storage stability test of the polyisocyanate mixture according to the invention at room temperature showed an NCO content of 8.30% and a viscosity of 975 mPa.s. after 150 days.
1308,2 g der Lösung des erfindungsgemäßen Polyisocyanatgemischs in NMP werden mit 40,1 g Dimethylethanolamin versetzt und während 5 Minuten verrührt.1308.2 g of the solution of the polyisocyanate mixture according to the invention in NMP are mixed with 40.1 g of dimethylethanolamine and stirred for 5 minutes.
Nach Zugabe von 1850 g entionisiertem Wasser entsteht eine milchig blaue, schwach durchsichtige wäßrige Dispersion mit einem Feststoffgehalt von 39,4 %, einer Viskosität (DIN 4-Becher) von 25 s bei einer mittleren Teilchengröße der dispergierten Partikel von 112 nm.After adding 1850 g of deionized water, a milky blue, slightly transparent aqueous dispersion with a solids content of 39.4%, a viscosity (DIN 4 cup) of 25 s and an average particle size of the dispersed particles of 112 nm is formed.
33 g eines hydroxyfunktionellen Polyacrylatharzes mit einem Hydroxylgruppengehalt von 4 % aus
30,6 Gew.-Teilen Hydroxyethylmethacrylat
17,4 Gew.-Teilen Methylmethacrylat
40,0 Gew.-Teilen Butylacrylat
8,0 Gew.-Teilen Acrylsäure
werden mit Ammoniaklösung und Wasser auf einen pH-Wert von 7,1 eingestellt, so daß eine 30 %ige Lösung des Polyacrylats in Wasser resultiert.33 g of a hydroxy-functional polyacrylate resin with a hydroxyl group content of 4%
30.6 parts by weight of hydroxyethyl methacrylate
17.4 parts by weight of methyl methacrylate
40.0 parts by weight of butyl acrylate
8.0 parts by weight of acrylic acid
are adjusted to a pH of 7.1 with ammonia solution and water, so that a 30% solution of the polyacrylate in water results.
Nach Zugabe von 0,3 g eines handelsüblichen Verdickers (®Acrysol RM 8 der Firma Rohm und Haas, Frankfurt) und 0,7 g eines handelsüblichen Entschäumers (®Foamex 1498 der Firma Goldschmidt AG, Essen) zu der wäßrigen Acrylatlösung werden 43,4 g der mit 3 g Dimethylethanolamin neutralisierten Lösung des Polyisocyanatgemisches gemäß Beispiel 2 zugegeben. Die Mischung ist durch bloßes Einrühren leicht zu homogenisieren.After adding 0.3 g of a commercially available thickener (®Acrysol RM 8 from Rohm and Haas, Frankfurt) and 0.7 g of a commercially available defoamer (®Foamex 1498 from Goldschmidt AG, Essen) to the aqueous acrylate solution, 43.4 g of the solution of the polyisocyanate mixture neutralized with 3 g of dimethylethanolamine according to Example 2 are added. The mixture is easy to homogenize by simply stirring it in.
Ein auf eine Glasplatte aufgetragener Film des Gemisches trocknet nach ca. 2 h bei Raumtemperatur bis zur Klebfreiheit und bildet einen klaren, glänzenden und störungsfreien Lackfilm, der nach vollständiger Aushärtung eine Pendelhärte nach König von 130 s aufweist. Nach einminütigem Einwirken von aliphatischen Kohlenwasserstoffen bleibt die Filmoberfläche unverändert. Bei ebenso langer Einwirkung von Xylol, Methoxypropylacetat und Ethanol erfolgt eine geringfügige Anquellung der Lackoberfläche, wobei nach Verdunsten der Lösungsmittel eine Regeneration des Films erfolgt.A film of the mixture applied to a glass plate dries after about 2 hours at room temperature until it is tack-free and forms a clear, glossy and trouble-free lacquer film which, after complete curing, has a König pendulum hardness of 130 s. After one minute of exposure to aliphatic hydrocarbons, the film surface remains unchanged. When xylene, methoxypropyl acetate and ethanol are exposed for an equally long time, the surface of the paint swells slightly, with the film regenerating after the solvents have evaporated.
Ein entsprechend, jedoch ohne Mitverwendung der erfindungsgemäßen Polyisocyanatlösung hergestellter Film quillt bereits bei Einwirken von aliphatischen Kohlenwasserstoffen deutlich an und ist in aromatischen Kohlenwasserstoffen oder Methoxypropylacetat leicht löslich.A film produced accordingly, but without the use of the polyisocyanate solution according to the invention, swells significantly even when exposed to aliphatic hydrocarbons and is readily soluble in aromatic hydrocarbons or methoxypropyl acetate.
Die Verarbeitungszeit des erfindungsgemäßen, die erfindungsgemäße Polyisocyanatlösung enthaltenden Zweikomponenten-Systems liegt bei ca. 4 h.The processing time of the two-component system according to the invention containing the polyisocyanate solution according to the invention is about 4 hours.
100 g der in Beispiel 3 beschriebenen wäßrigen Polyacrylatlösung, der ebenso wie in Beispiel 3 Verdicker und Entschäumer zugegeben worden sind, werden mit 30,4 g eines Polyisocyanatgemisches homogenisiert. Bei dem Polyisocyanatgemisch handelt es sich um ein Gemisch aus 15,2 g eines Isocyanuratgruppen aufweisenden Polyisocyanats auf Basis von 1,6-Diisocyanatohexan mit einer NCO-Funktionalität von 3,5, einem NCO-Gehalt von 21,7 % und einer Viskosität bei 23°C von 1.500 mPa.s und 15,2 g des Polyisocyanatgemisches gemäß Beispiel 2, welches vorab mit 1,3 g N,N-Dimethylethanolamin neutralisiert worden ist.100 g of the aqueous polyacrylate solution described in Example 3, to which thickeners and defoamers have been added, as in Example 3, are homogenized with 30.4 g of a polyisocyanate mixture. The polyisocyanate mixture is a mixture of 15.2 g of a polyisocyanate containing isocyanurate groups and based on 1,6-diisocyanatohexane with an NCO functionality of 3.5, an NCO content of 21.7% and a viscosity at 23 ° C of 1,500 mPa.s and 15.2 g of the polyisocyanate mixture according to Example 2, which has been neutralized beforehand with 1.3 g of N, N-dimethylethanolamine.
Es liegt ein NCO/OH-Äquivalentverhältnis von 1,5:1 vor. Ein aus der Formulierung gewonnener Lackfilm ist nach 2 h bei Raumtemperatur klebfrei, hochglänzend und störungsfrei. Bei alleiniger Aushärtung des Polyacrylatharzes mit dem genannten, Isocyanuratgruppen aufweisenden Polyisocyanat ergeben sich Filme mit deutlicher Trübung und vermindertem Glanz.There is an NCO / OH equivalent ratio of 1.5: 1. A paint film obtained from the formulation is tack-free, high-gloss and trouble-free after 2 hours at room temperature. If the polyacrylate resin is cured solely with the polyisocyanate mentioned, which has isocyanurate groups, films are obtained with a clear cloudiness and reduced gloss.
Der erfindungsgemäße Lackfilm weist nach Aushärten bei Raumtemperatur eine Härte nach König von 150 s auf. Bei einminütigem Einwirken von aliphatischen oder aromatischen Kohlenwasserstoffen oder von Methoxypropylacetat zeigt sich keine Veränderung der Filmoberfläche. Bei Einwirkung von Ethanol während des gleichen Zeitraumes erfolgt eine geringfügige, nach Verdunsten des Lösungsmittels reversible Anquellung.After curing at room temperature, the lacquer film according to the invention has a König hardness of 150 s. At 1 minute exposure to aliphatic or aromatic hydrocarbons or methoxypropyl acetate shows no change in the film surface. When ethanol is exposed for the same period of time, there is a slight swelling that is reversible after the solvent has evaporated.
1500 g Hexamethylendiisocyanat (HDI) werden mit 60 g Dimethylpropionsäure (DMPS) vermischt und auf 55°C erwärmt. Nach Zugabe von 4,5 g Tri-n-butylphosphin und 4 h Rühren bei 60°C ist der NCO-Gehalt der klaren Lösung auf 37,5 % abgesunken.1500 g of hexamethylene diisocyanate (HDI) are mixed with 60 g of dimethylpropionic acid (DMPS) and heated to 55 ° C. After adding 4.5 g of tri-n-butylphosphine and stirring for 4 hours at 60 ° C., the NCO content of the clear solution has dropped to 37.5%.
Die Reaktion wird dann durch Zugabe von 4,1 g p-Toluolsulfonsäuremethylester (TSE) und einstündiges Nachrühren bei 80°C gestoppt.The reaction is then stopped by adding 4.1 g of p-toluenesulfonic acid methyl ester (TSE) and stirring at 80 ° C. for one hour.
Das überschüssige HDI wird anschließend durch Vakuumdestillation über einen Kurzwegverdampfer bei 150°C/0,05 mbar aus der Rohwarelösung entfernt.The excess HDI is then removed from the raw material solution by vacuum distillation using a short-path evaporator at 150 ° C./0.05 mbar.
Das in quantitativer Ausbeute erhaltene Carboxylpolyisocyanatgemisch hat folgende charakteristische Daten:
Die Überprüfung der Lagerstabilität des erfindungsgemäßen, eingebaute Carboxylgruppen tragenden Polyisocyanatgruppengemisches ergab nach 150 Tagen bei Raumtemperatur einen NCO-Gehalt von 18,8 % und eine Viskosität von 2110 mPas (23°C).Examination of the storage stability of the built-in carboxyl group-bearing polyisocyanate group mixture according to the invention showed an NCO content of 18.8% and a viscosity of 2110 mPas (23 ° C.) after 150 days at room temperature.
Auf einer Glasplatte trocknet das erfindungsgemäße 100 %ige Polyisocyanatgemisch nach 1 h bei Raumtemperatur oder 30 Min. bei 140°C zu einem klaren, rißfreien und staubtrockenen Film.The 100% polyisocyanate mixture according to the invention dries on a glass plate after 1 hour at room temperature or 30 minutes at 140 ° C. to form a clear, crack-free and dust-dry film.
Die Pendelhärte nach König beträgt für den bei Raumtemperatur getrockneten Film 60 s, für den hitzegehärteten 85 s.The König pendulum hardness is 60 s for the film dried at room temperature and 85 s for the heat-cured film.
200 g des beschriebenen Polyisocyanatgemisches werden mit 10 g N-Dimethylethanolamin versetzt und in 190 g entionisiertem Wasser dispergiert. Es entsteht eine schwach blaue wäßrige Polyurethan-Harnstoffdispersion, die bis zum Ende der Gasentwicklung nachgerührt wird und folgede charakteristische Daten aufweist:
1100 g HDI und 373 g Isophorondiisocyanat (IPDI) werden mit 60 g DMPS vermischt und auf 55°C erwärmt.1100 g HDI and 373 g isophorone diisocyanate (IPDI) are mixed with 60 g DMPS and heated to 55 ° C.
Nach Zugabe von 4,5 g Tri-n-butylphosphin und 5 h Rühren bei 60°C ist der NCO-Gehalt der klaren Lösung auf 35,0 % gesunken.After adding 4.5 g of tri-n-butylphosphine and stirring for 5 hours at 60 ° C., the NCO content of the clear solution has dropped to 35.0%.
Die Reaktion wird dann durch Zugabe von 4,1 g TSE und einstündiges Nachrühren bei 80°C abgestoppt.The reaction is then stopped by adding 4.1 g of TSE and stirring at 80 ° C. for one hour.
Das überschüssige monomere Diisocyanatgemisch wird, wie in Beispiel 5 beschrieben, destilliert.The excess monomeric diisocyanate mixture is distilled as described in Example 5.
Das erhaltene Carboxylpolyisocyanatgemisch weist folgende charakteristische Daten auf:
Die Überprüfung der Lagerstabilität des erfindungsgemäßen Carboxylpolyisocyanats ergab nach 150 Tagen bei Raumtemperatur einen NCO-Gehalt von 18,2 % und eine Viskosität von 3295 mPas.The examination of the storage stability of the carboxyl polyisocyanate according to the invention showed an NCO content of 18.2% and a viscosity of 3295 mPas after 150 days at room temperature.
Auf einer Glasplatte trocknet das erfindungsgemäße Carboxylpolyisocyanat nach 1 h bei Raumtemperatur oder 30 Min. bei 140°C zu einem klaren rißfreien Film.The carboxyl polyisocyanate according to the invention dries on a glass plate after 1 hour at room temperature or 30 minutes at 140 ° C. to form a clear, crack-free film.
Die Pendelhärten nach König betragen nach Raumtemperaturtrocknung 80 s, für den ofengetrockneten 98 s.The König pendulum hardness after drying at room temperature is 80 s, for the oven-dried 98 s.
505,4 g des in Beispiel 1 beschriebenen Ausgangspolyisocyanats auf der Basis von HDI werden mit 579,0 g eines Uretdion-/Isocyanuratpolyisocyanats auf der Basis von 1-Isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexan (IPDI) abgemischt.505.4 g of the starting polyisocyanate based on HDI described in Example 1 are mixed with 579.0 g of a uretdione / isocyanurate polyisocyanate based on 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (IPDI) mixed.
Die entstandene klare Lösung hat einen NCO-Gehalt von 20,2 %, eine Viskosität von 1320 mPas (23°C) und eine mittlere Funktionalität von 2.3.
wird bei 74°C solange gerührt, bis der NCO-Gehalt des Reaktionsgemisches auf 14,9 % abgesunken ist.The resulting clear solution has an NCO content of 20.2%, a viscosity of 1320 mPas (23 ° C) and an average functionality of 2.3.
is stirred at 74 ° C until the NCO content of the reaction mixture has dropped to 14.9%.
Charakteristische Daten des erfindungsgemäßen Polyisocyanatgemisches :
Die wie in Beispiel 1 hergestellten und getrockneten Filme des erfindungsgemäßen Polyisocyanatgemisches sind klar und homogen.The films of the polyisocyanate mixture according to the invention prepared and dried as in Example 1 are clear and homogeneous.
Die Pendelhärten nach König liegen nach 2 h Raumtemperaturtrocknung bei 85 s und nach 30 min Ofentrocknung bei 108 s. Nach einminütigem Einwirken von aliphatischen und aromatischen Kohlenwasserstoffen und Methoxypropylacetat bleibt die Filmoberfläche des ausgehärteten Polyisocyanatgemisches unverändert.The König pendulum hardness is 85 s after 2 h room temperature drying and 108 s after 30 min oven drying. After one minute of exposure to aliphatic and aromatic hydrocarbons and methoxypropyl acetate, the film surface of the cured polyisocyanate mixture remains unchanged.
Die Überprüfung der Lagerstabilität des Polyisocyanatgemisches ergab nach 150 Tagen bei Raumtemperatur einen NCO-Gehalt von 14,6 % und eine Viskosität von 1811 mPas (23°C).The examination of the storage stability of the polyisocyanate mixture showed an NCO content of 14.6% and a viscosity of 1811 mPas (23 ° C.) after 150 days at room temperature.
Nach Zugabe von Wasser im Überschuß lassen sich die erfindungsgemäßen Polyisocyanate wie in Beispiel 1 beschrieben, spontan dispergieren.After adding water in excess, the polyisocyanates according to the invention can be dispersed spontaneously as described in Example 1.
Claims (5)
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DE4001783 | 1990-01-23 | ||
DE4001783A DE4001783A1 (en) | 1990-01-23 | 1990-01-23 | POLYISOCYANATE MIXTURES, A PROCESS FOR THEIR PRODUCTION AND THEIR USE AS A BINDER FOR COATING AGENTS OR AS A REACTION PARTNER FOR ISOCYANATE GROUPS OR CARBOXYL GROUPS REACTIVE COMPOUNDS |
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EP90124222A Withdrawn EP0443138A1 (en) | 1990-01-23 | 1990-12-14 | Polyisocyanate mixtures, process for their preparation and their use as a binder for coating-compositions or as a reaction component for compounds reactive with isocyanate groups or carboxylic groups |
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EP (1) | EP0443138A1 (en) |
JP (1) | JPH04211418A (en) |
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Cited By (25)
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EP0510438A2 (en) * | 1991-04-23 | 1992-10-28 | Bayer Ag | Polyisocyanate blends and their use |
EP0510438A3 (en) * | 1991-04-23 | 1993-01-07 | Bayer Ag | Polyisocyanate blends, a process for their preparation and their use |
EP0548669A2 (en) * | 1991-12-20 | 1993-06-30 | Bayer Ag | Isocyanato carboxylic acids, a method for their preparation and their use |
EP0548669A3 (en) * | 1991-12-20 | 1993-08-11 | Bayer Ag | Isocyanato carboxylic acids, a method for their preparation and their use |
EP0568134A1 (en) * | 1992-04-16 | 1993-11-03 | Akzo Nobel N.V. | Aqueous coating compositions |
AU663933B2 (en) * | 1992-04-16 | 1995-10-26 | Akzo N.V. | Aqueous coating compositions |
TR28102A (en) * | 1992-04-16 | 1995-12-27 | Akzo Nv | Aqueous coating compositions containing a resin resin-capable resin component. |
EP0566953A1 (en) * | 1992-04-24 | 1993-10-27 | Bayer Ag | Aqueous coating compositions for elastic stoving lacquers |
EP0907673A1 (en) * | 1996-05-30 | 1999-04-14 | ARCO Chemical Technology, L.P. | Two-component waterborne polyurethane coating |
EP0907673A4 (en) * | 1996-05-30 | 1999-11-10 | Arco Chem Tech | Two-component waterborne polyurethane coating |
EP1362875A1 (en) * | 2002-05-11 | 2003-11-19 | Degussa AG | Bifunctional polyaddition compounds as crosslinkers for polyurethane powder coatings |
US6849705B2 (en) | 2002-05-11 | 2005-02-01 | Degussa Ag | Bifunctional polyaddition compounds as crosslinkers for polyurethane powder coatings |
EP1687354A1 (en) * | 2003-11-25 | 2006-08-09 | Basf Corporation | A method for making an aqueous coating with a solid crosslinking agent |
WO2011144644A1 (en) | 2010-05-21 | 2011-11-24 | Evonik Degussa Gmbh | Hydrophilic polyisocyanates |
DE102010029235A1 (en) | 2010-05-21 | 2011-11-24 | Evonik Degussa Gmbh | Hydrophilic polyisocyanates |
DE102012218081A1 (en) | 2012-10-04 | 2014-04-10 | Evonik Industries Ag | Novel hydrophilic polyisocyanates with improved storage stability |
WO2014053269A1 (en) | 2012-10-04 | 2014-04-10 | Evonik Industries Ag | Storage-stable hydrophilic polyisocyanates |
WO2015035673A1 (en) | 2013-09-13 | 2015-03-19 | 万华化学集团股份有限公司 | Polyisocyanate modified with sulphamic acid, preparation method therefor and use thereof |
US9975985B2 (en) | 2013-09-13 | 2018-05-22 | Wanhua Chemical Group Co., Ltd. | Polyisocyanate modified with sulphamic acid, preparation method thereof and use thereof |
DE102014209183A1 (en) | 2014-05-15 | 2015-11-19 | Evonik Degussa Gmbh | Reactive composition of a dispersion containing uretdione groups and polyamines |
EP2947106A1 (en) | 2014-05-15 | 2015-11-25 | Evonik Industries AG | Reactive composition comprising dispersion and polyamines containing uretdiones |
WO2020109189A1 (en) | 2018-11-30 | 2020-06-04 | Covestro Deutschland Ag | Modified polyisocyanate |
WO2022069561A1 (en) | 2020-09-30 | 2022-04-07 | Covestro Deutschland Ag | A modified polyisocyanate |
EP4001332A1 (en) | 2020-11-18 | 2022-05-25 | Covestro Deutschland AG | A modified polyisocyanate |
EP4015554A1 (en) | 2020-12-17 | 2022-06-22 | Covestro Deutschland AG | Water-dispersible modified polyisocyanates |
Also Published As
Publication number | Publication date |
---|---|
US5098983A (en) | 1992-03-24 |
KR910014423A (en) | 1991-08-31 |
CA2033741A1 (en) | 1991-07-24 |
JPH04211418A (en) | 1992-08-03 |
DE4001783A1 (en) | 1991-07-25 |
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